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Register a new userSlip-Mediated Dewetting of Polymer Microdroplets
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Classical hydrodynamic models predict that infinite work is required to move a three-phase contact line, defined here as the line where a liquid/vapor interface intersects a solid surface. Assuming a slip boundary condition, in which the liquid slides against the solid, such an unphysical prediction is avoided. In this article, we present the results of experiments in which a contact line moves and where slip is a dominating and controllable factor. Spherical cap shaped polystyrene microdroplets, with non-equilibrium contact angle, are placed on solid self-assembled monolayer coatings from which they dewet. The relaxation is monitored using textit{in situ} atomic force microscopy. We find that slip has a strong influence on the droplet evolutions, both on the transient non-spherical shapes and contact line dynamics. The observations are in agreement with scaling analysis and boundary element numerical integration of the governing Stokes equations, including a Navier slip boundary condition.
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Hydrodynamic slip of a liquid at a solid surface represents a fundamental phenomenon in fluid dynamics that governs liquid transport at small scales. For polymeric liquids, de Gennes predicted that the Navier boundary condition together with the theory of polymer dynamics imply extraordinarily large interfacial slip for entangled polymer melts on ideal surfaces; this Navier-de Gennes model was confirmed using dewetting experiments on ultra-smooth, low-energy substrates. Here, we use capillary leveling - surface tension driven flow of films with initially non-uniform thickness - of polymeric films on these same substrates. Measurement of the slip length from a robust one-parameter fit to a lubrication model is achieved. We show that at the lower shear rates involved in leveling experiments as compared to dewetting ones, the employed substrates can no longer be considered ideal. The data is instead consistent with physical adsorption of polymer chains at the solid/liquid interface. We extend the Navier-de Gennes description using one additional parameter, namely the density of physically adsorbed chains per unit surface. The resulting formulation is found to be in excellent agreement with the experimental observations.
Surface roughness becomes relevant if typical length scales of the system are comparable to the scale of the variations as it is the case in microfluidic setups. Here, an apparent boundary slip is often detected which can have its origin in the assumption of perfectly smooth boundaries. We investigate the problem by means of lattice Boltzmann (LB) simulations and introduce an ``effective no-slip plane at an intermediate position between peaks and valleys of the surface. Our simulations show good agreement with analytical results for sinusoidal boundaries, but can be extended to arbitrary geometries and experimentally obtained surface data. We find that the detected apparent slip is independent of the detailed boundary shape, but only given by the distribution of surface heights. Further, we show that the slip diverges as the amplitude of the roughness increases.
We study theoretically the surface response of a semi-infinite viscoelastic polymer network using the two-fluid model. We focus on the overdamped limit and on the effect of the networks intrinsic length scales. We calculate the decay rate of slow surface fluctuations, and the surface displacement in response to a localized force. Deviations from the large-scale continuum response are found at length scales much larger than the networks mesh size. We discuss implications for surface scattering and microrheology. We provide closed-form expressions that can be used for surface microrheology -- the extraction of viscoelastic moduli and intrinsic length scales from the motions of tracer particles lying on the surface without doping the bulk material.
We investigate the effect of short chains on slip of highly entangled polystyrenes (PS) during thin film dewetting from non-wetting fluorinated surfaces. Binary and ternary mixtures were prepared from monodisperse PS with weight average molecular weights $5 < M_textrm{w} < 490$ kg/mol. Flow dynamics and rim morphology of dewetting holes were captured using optical and atomic force microscopy. Slip properties are assessed in the framework of hydrodynamic models describing the rim height profile of dewetting holes. We show that short chains with $M_textrm{w}$ below the polymer critical molecular weight for entanglements, $M_textrm{c}$, can play an important role in slip of highly entangled polymers. Among mixtures of the same $M_textrm{w}$, those containing chains with $M<M_textrm{c}$ exhibit larger slip lengths as the number average molecular weight, $M_textrm{n}$, decreases. The slip enhancement effect is only applicable when chains with $M<M_textrm{c}$ are mixed with highly entangled chains such that the content of the long chain component, $phi_textrm{L}$, is dominant ($phi_textrm{L}<0.5$). These results suggest that short chains affect slip of highly entangled polymers on non-wetting surfaces due to the physical or chemical disparities of end groups, and any associated dynamical effect their presence may have, as compared to the backbone units. The enhanced slip in this regard is attributed to the impact of chain end groups or short chain enrichment on the effective interfacial friction coefficient. Accordingly, for entangled PS, a higher concentration of end groups or short chains at the interface results in a lower effective friction coefficient which consequently enhances the slip length.
This study reveals the influence of the surface energy and solid/liquid boundary condition on the breakup mechanism of dewetting ultra-thin polymer films. Using silane self-assembled monolayers, SiO$_2$ substrates are rendered hydrophobic and provide a strong slip rather than a no-slip solid/liquid boundary condition. On undergoing these changes, the thin-film breakup morphology changes dramatically -- from a spinodal mechanism to a breakup which is governed by nucleation and growth. The experiments reveal a dependence of the hole density on film thickness and temperature. The combination of lowered surface energy and hydrodynamic slip brings the studied system closer to the conditions encountered in bursting unsupported films. As for unsupported polymer films, a critical nucleus size is inferred from a free energy model. This critical nucleus size is supported by the film breakup observed in the experiments using high speed emph{in situ} atomic force microscopy.
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